CN112662177B - High-modulus and high-hardness polyimide film - Google Patents
High-modulus and high-hardness polyimide film Download PDFInfo
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- CN112662177B CN112662177B CN202011373747.3A CN202011373747A CN112662177B CN 112662177 B CN112662177 B CN 112662177B CN 202011373747 A CN202011373747 A CN 202011373747A CN 112662177 B CN112662177 B CN 112662177B
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 83
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000004642 Polyimide Substances 0.000 claims abstract description 38
- 230000004048 modification Effects 0.000 claims abstract description 15
- 238000012986 modification Methods 0.000 claims abstract description 15
- 230000033444 hydroxylation Effects 0.000 claims abstract description 13
- 238000005805 hydroxylation reaction Methods 0.000 claims abstract description 13
- -1 pyrimidone diamine Chemical class 0.000 claims abstract description 10
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims abstract description 9
- 150000004985 diamines Chemical class 0.000 claims abstract description 7
- 239000011159 matrix material Substances 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 150000004984 aromatic diamines Chemical class 0.000 claims description 5
- LJMPOXUWPWEILS-UHFFFAOYSA-N 3a,4,4a,7a,8,8a-hexahydrofuro[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1C2C(=O)OC(=O)C2CC2C(=O)OC(=O)C21 LJMPOXUWPWEILS-UHFFFAOYSA-N 0.000 claims description 4
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 claims description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 claims description 3
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 claims description 3
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 claims description 3
- BUXQSBATTZNERM-UHFFFAOYSA-N 2,5-diamino-1h-pyrimidin-6-one Chemical group NC1=CN=C(N)N=C1O BUXQSBATTZNERM-UHFFFAOYSA-N 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004005 microsphere Substances 0.000 abstract description 31
- 239000000377 silicon dioxide Substances 0.000 abstract description 28
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 27
- 239000000243 solution Substances 0.000 description 76
- 238000003756 stirring Methods 0.000 description 55
- 239000000203 mixture Substances 0.000 description 51
- 238000006243 chemical reaction Methods 0.000 description 32
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 28
- 238000001035 drying Methods 0.000 description 27
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- 238000001914 filtration Methods 0.000 description 20
- 239000011521 glass Substances 0.000 description 15
- 229920005575 poly(amic acid) Polymers 0.000 description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000012024 dehydrating agents Substances 0.000 description 7
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 7
- 238000001132 ultrasonic dispersion Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- VTGOHKSTWXHQJK-UHFFFAOYSA-N pyrimidin-2-ol Chemical group OC1=NC=CC=N1 VTGOHKSTWXHQJK-UHFFFAOYSA-N 0.000 description 2
- YCIPQJTZJGUXND-UHFFFAOYSA-N Aglaia odorata Alkaloid Natural products C1=CC(OC)=CC=C1C1(C(C=2C(=O)N3CCCC3=NC=22)C=3C=CC=CC=3)C2(O)C2=C(OC)C=C(OC)C=C2O1 YCIPQJTZJGUXND-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000004523 agglutinating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention provides a high-modulus high-hardness polyimide film, which comprises a polyimide matrix and silicon dioxide microspheres dispersed in the polyimide matrix; the polyimide is obtained by performing polycondensation reaction on diamine monomers including pyrimidone diamine and tetracarboxylic dianhydride, and the silica microspheres are silica microspheres with surface hydroxylation modification. The high-modulus and high-hardness polyimide film provided by the invention has the performance advantages of high modulus and high hardness.
Description
Technical Field
The invention relates to the technical field of polyimide, in particular to a high-modulus and high-hardness polyimide film.
Background
In recent years, with the thinning, high computing capability and high storage capability of smart phones and tablet computers, the requirements for polyimide film materials, such as higher modulus, lower shrinkage, more excellent three-dimensional stability, more excellent heat conductivity, etc., are increasing. The performance can be obtained by the combination and modification of the inorganic nano material and the organic material.
Chinese patent CN101289542A provides a method for polymerization modification by adopting spherical powder silicon dioxide and a polyimide body, but the method has the defects that the viscosity of polyamic acid solution is high, and the agglomeration of nano particles is serious in a physical dispersion method under the high viscosity state, so that the prepared silicon dioxide composite polyimide film has large inorganic particle size and poor dispersion size, and the performance of the product is greatly damaged.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a high-modulus and high-hardness polyimide film which can have the performance advantages of high modulus and high hardness.
The invention provides a high-modulus high-hardness polyimide film, which comprises a polyimide matrix and silicon dioxide microspheres dispersed in the polyimide matrix;
the polyimide is obtained by performing polycondensation reaction on diamine monomers including pyrimidone diamine and tetracarboxylic dianhydride, and the silica microspheres are silica microspheres with surface hydroxylation modification.
Preferably, the silica microspheres are 1-28 wt% of the polyimide weight.
Preferably, the pyrimidinone diamine is 2, 5-diaminopyrimidin-4 (3H) -one.
Preferably, the diamine monomer further includes an aromatic diamine, which is preferably at least one of 4, 4' -diaminodiphenyl ether, 1, 3-bis (4' -aminophenoxy) benzene, 4' -diaminodiphenyl sulfide, 4' -diaminodiphenylmethane, 3' -diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfone, or 4, 4' -diaminobenzophenone.
Preferably, the molar ratio of pyrimidone diamine to aromatic diamine is 1: 0.5-4.
Preferably, the tetracarboxylic dianhydride is at least one of 4, 4'- (hexafluoroisopropylidene) diphthalic anhydride, 3, 3', 4, 4 '-biphenyltetracarboxylic dianhydride, 4, 4' -oxydiphthalic dianhydride, 2', 3, 3' -benzophenonetetracarboxylic dianhydride, 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride, or 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride.
Preferably, the silica microspheres with surface hydroxylation modification are obtained by reacting silica microspheres with an alkali compound.
Preferably, the alkali compound is sodium hydroxide or potassium hydroxide.
Preferably, the high-modulus high-hardness polyimide film is prepared by adopting the following method: performing polycondensation reaction on a diamine monomer containing pyrimidone diamine and tetracarboxylic dianhydride to obtain polyimide, fully mixing the polyimide and the silica microspheres with surface hydroxylation modification, and forming a film to obtain the polyimide film.
The polyimide film of the invention adopts polyimide obtained by the polycondensation of pyrimidone diamine and tetracarboxylic dianhydride as a matrix, silica microspheres with surface hydroxylation modification as a filler, therefore, the corresponding polyimide contains a pyrimidone structure, the surface of the silicon dioxide microsphere has a hydroxyl structure, therefore, when the two are mixed, the pyrimidone structure of the polyimide and the hydroxyl on the surface of the silicon dioxide microsphere can form hydrogen bond action, so that a stronger chemical bond action exists between the polyimide organic phase and the silicon dioxide inorganic phase, thus not only enhancing the dispersibility of the silica microspheres in the polyimide, but also preventing the silica microspheres from agglutinating, therefore, the dispersion stability of the silica particle microspheres in the polyimide is effectively improved, and the polyimide film can obtain the performance advantages of high modulus and high hardness.
In the present invention, the hydrogen bonding between the polyimide and the silica microspheres can be schematically illustrated by referring to the following structures:
Detailed Description
Hereinafter, the technical solution of the present invention will be described in detail by specific examples, but these examples should be explicitly proposed for illustration, but should not be construed as limiting the scope of the present invention.
Example 1
A high-modulus high-hardness polyimide film is prepared by the following steps:
s1, adding 2.0mL of ammonia water (25%) into 30mL of ethanol water solution with the volume ratio of 4:1, uniformly stirring, adding 30mL of anhydrous ethanol in which 1.1mL of tetraethoxysilane is dissolved, stirring for reacting for 5 hours to obtain silicon dioxide microsphere sol, washing, filtering, and drying at 60 ℃ for 12 hours to obtain silicon dioxide microspheres;
adding 1g of silicon dioxide microspheres into 10mL of sodium hydroxide aqueous solution (10 wt%), stirring in a water bath at 80 ℃ for reaction for 2h, cooling to room temperature after the reaction is finished, filtering, washing with water, and drying at 60 ℃ for 12h to obtain surface-hydroxylated modified silicon dioxide microspheres;
s2, under nitrogen atmosphere, adding 12.6g (100mmol) of 2, 5-diaminopyrimidin-4 (3H) -ketone into 200mL of anhydrous N, N-dimethylacetamide (DMAc) and uniformly stirring, then adding 44.4g (100mol) of 4, 4' - (hexafluoroisopropylene) diphthalic anhydride and stirring for reaction for 3 hours at room temperature to obtain a polyamic acid solution; continuously stirring the polyamic acid solution for 6 hours, adding 6.5mL of pyridine serving as an imidizing agent, adding 19.5mL of acetic anhydride serving as a dehydrating agent after complete dispersion, stirring for reaction for 3 hours, adding the obtained reaction solution into ethanol for precipitation, filtering, and drying at 100 ℃ overnight to obtain polyimide;
s3, adding 1g of silica microspheres with surface hydroxylation modification into 60mL of anhydrous N, N-dimethylacetamide (DMAc) for uniform ultrasonic dispersion, adding 10g of the polyimide, stirring and mixing for 2h to obtain a mixture solution, performing vacuum defoaming treatment on the mixture solution, coating the mixture solution on a glass plate, treating the mixture solution at 60 ℃ for 30min, drying the mixture solution at 150 ℃ for 60min, peeling the mixture from the glass plate, fixing the mixture solution on a metal frame, placing the metal frame in a vacuum drying oven, treating the mixture solution at 280 ℃ for 60min, and cooling to obtain the polyimide film, wherein the thickness of the polyimide film is controlled to be 50 microns.
Example 2
A high-modulus high-hardness polyimide film is prepared by the following steps:
s1, adding 2.0mL of ammonia water (25%) into 30mL of ethanol water solution with the volume ratio of 4:1, uniformly stirring, adding 30mL of anhydrous ethanol in which 1.1mL of tetraethoxysilane is dissolved, stirring for reacting for 5 hours to obtain silicon dioxide microsphere sol, washing, filtering, and drying at 60 ℃ for 12 hours to obtain silicon dioxide microspheres;
adding 1g of silicon dioxide microspheres into 10mL of sodium hydroxide aqueous solution (10 wt%), stirring in a water bath at 80 ℃ for reaction for 2h, cooling to room temperature after the reaction is finished, filtering, washing with water, and drying at 60 ℃ for 12h to obtain surface-hydroxylated modified silicon dioxide microspheres;
s2, under nitrogen atmosphere, adding 5.04g (40mmol) of 2, 5-diaminopyrimidin-4 (3H) -ketone and 12.0g (60mmol) of 4, 4 '-diaminodiphenyl ether into 200mL of anhydrous N, N-dimethylacetamide (DMAc) and uniformly stirring, then adding 44.4g (100mol) of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride and stirring for reaction for 3H at room temperature to obtain a polyamic acid solution; continuously stirring the polyamic acid solution for 6 hours, adding 6.5mL of pyridine serving as an imidizing agent, adding 19.5mL of acetic anhydride serving as a dehydrating agent after complete dispersion, stirring for reaction for 3 hours, adding the obtained reaction solution into ethanol for precipitation, filtering, and drying at 100 ℃ overnight to obtain polyimide;
s3, adding 1g of silica microspheres with surface hydroxylation modification into 60mL of anhydrous N, N-dimethylacetamide (DMAc) for uniform ultrasonic dispersion, adding 10g of the polyimide, stirring and mixing for 2h to obtain a mixture solution, performing vacuum defoaming treatment on the mixture solution, coating the mixture solution on a glass plate, treating the mixture solution at 60 ℃ for 30min, drying the mixture solution at 150 ℃ for 60min, peeling the mixture from the glass plate, fixing the mixture solution on a metal frame, placing the metal frame in a vacuum drying oven, treating the mixture solution at 280 ℃ for 60min, and cooling to obtain the polyimide film, wherein the thickness of the polyimide film is controlled to be 50 microns.
Example 3
A high-modulus high-hardness polyimide film is prepared by the following steps:
s1, adding 2.0mL of ammonia water (25%) into 30mL of ethanol water solution with the volume ratio of 4:1, uniformly stirring, adding 30mL of anhydrous ethanol in which 1.1mL of tetraethoxysilane is dissolved, stirring for reacting for 5 hours to obtain silicon dioxide microsphere sol, washing, filtering, and drying at 60 ℃ for 12 hours to obtain silicon dioxide microspheres;
adding 1g of silicon dioxide microspheres into 10mL of sodium hydroxide aqueous solution (10 wt%), stirring in a water bath at 80 ℃ for reaction for 2h, cooling to room temperature after the reaction is finished, filtering, washing with water, and drying at 60 ℃ for 12h to obtain surface-hydroxylated modified silicon dioxide microspheres;
s2, under nitrogen atmosphere, adding 5.04g (40mmol) of 2, 5-diaminopyrimidin-4 (3H) -ketone and 12.0g (60mmol) of 4, 4 '-diaminodiphenyl ether into 200mL of anhydrous N, N-dimethylacetamide (DMAc) and uniformly stirring, then adding 44.4g (100mol) of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride and stirring for reaction for 3H at room temperature to obtain a polyamic acid solution; continuously stirring the polyamic acid solution for 6 hours, adding 6.5mL of pyridine serving as an imidizing agent, adding 19.5mL of acetic anhydride serving as a dehydrating agent after complete dispersion, stirring for reaction for 3 hours, adding the obtained reaction solution into ethanol for precipitation, filtering, and drying at 100 ℃ overnight to obtain polyimide;
s3, adding 2g of silica microspheres with surface hydroxylation modification into 60mL of anhydrous N, N-dimethylacetamide (DMAc) for uniform ultrasonic dispersion, adding 10g of the polyimide, stirring and mixing for 2h to obtain a mixture solution, performing vacuum defoaming treatment on the mixture solution, coating the mixture solution on a glass plate, treating the mixture solution at 60 ℃ for 30min, drying the mixture solution at 150 ℃ for 60min, peeling the mixture from the glass plate, fixing the mixture solution on a metal frame, placing the metal frame in a vacuum drying oven, treating the mixture solution at 280 ℃ for 60min, and cooling to obtain the polyimide film, wherein the thickness of the polyimide film is controlled to be 50 microns.
Example 4
A high-modulus high-hardness polyimide film is prepared by the following steps:
s1, adding 2.0mL of ammonia water (25%) into 30mL of ethanol water solution with the volume ratio of 4:1, uniformly stirring, adding 30mL of anhydrous ethanol in which 1.1mL of tetraethoxysilane is dissolved, stirring for reacting for 5 hours to obtain silicon dioxide microsphere sol, washing, filtering, and drying at 60 ℃ for 12 hours to obtain silicon dioxide microspheres;
adding 1g of silicon dioxide microspheres into 10mL of sodium hydroxide aqueous solution (10 wt%), stirring in a water bath at 80 ℃ for reaction for 2h, cooling to room temperature after the reaction is finished, filtering, washing with water, and drying at 60 ℃ for 12h to obtain surface-hydroxylated modified silicon dioxide microspheres;
s2, under nitrogen atmosphere, adding 5.04g (40mmol) of 2, 5-diaminopyrimidin-4 (3H) -ketone and 17.5g (60mmol) of 1, 3-bis (4' -aminophenoxy) benzene into 200mL of anhydrous N, N-dimethylacetamide (DMAc) and uniformly stirring, then adding 29.4g (100mol) of 3, 3', 4, 4' -biphenyltetracarboxylic dianhydride and stirring for reaction for 3 hours at room temperature to obtain a polyamic acid solution; continuously stirring the polyamic acid solution for 6 hours, adding 6.5mL of pyridine serving as an imidizing agent, adding 19.5mL of acetic anhydride serving as a dehydrating agent after complete dispersion, stirring for reaction for 3 hours, adding the obtained reaction solution into ethanol for precipitation, filtering, and drying at 100 ℃ overnight to obtain polyimide;
s3, adding 1g of silica microspheres with surface hydroxylation modification into 60mL of anhydrous N, N-dimethylacetamide (DMAc) for uniform ultrasonic dispersion, adding 10g of the polyimide, stirring and mixing for 2h to obtain a mixture solution, performing vacuum defoaming treatment on the mixture solution, coating the mixture solution on a glass plate, treating the mixture solution at 60 ℃ for 30min, drying the mixture solution at 150 ℃ for 60min, peeling the mixture from the glass plate, fixing the mixture solution on a metal frame, placing the metal frame in a vacuum drying oven, treating the mixture solution at 280 ℃ for 60min, and cooling to obtain the polyimide film, wherein the thickness of the polyimide film is controlled to be 50 microns.
Example 5
A high-modulus high-hardness polyimide film is prepared by the following steps:
s1, adding 2.0mL of ammonia water (25%) into 30mL of ethanol water solution with the volume ratio of 4:1, uniformly stirring, adding 30mL of anhydrous ethanol in which 1.1mL of tetraethoxysilane is dissolved, stirring for reacting for 5 hours to obtain silicon dioxide microsphere sol, washing, filtering, and drying at 60 ℃ for 12 hours to obtain silicon dioxide microspheres;
adding 1g of silicon dioxide microspheres into 10mL of sodium hydroxide aqueous solution (10 wt%), stirring in a water bath at 80 ℃ for reaction for 2h, cooling to room temperature after the reaction is finished, filtering, washing with water, and drying at 60 ℃ for 12h to obtain surface-hydroxylated modified silicon dioxide microspheres;
s2, under the nitrogen atmosphere, adding 5.04g (40mmol) of 2, 5-diaminopyrimidine-4 (3H) -ketone and 12.0g (60mmol) of 4, 4' -diaminodiphenyl ether into 200mL of anhydrous N, N-dimethylacetamide (DMAc) and uniformly stirring, then adding 22.4g (100mol) of 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride and stirring at room temperature for reacting for 3 hours to obtain a polyamic acid solution; continuously stirring the polyamic acid solution for 6 hours, adding 6.5mL of pyridine serving as an imidizing agent, adding 19.5mL of acetic anhydride serving as a dehydrating agent after complete dispersion, stirring for reaction for 3 hours, adding the obtained reaction solution into ethanol for precipitation, filtering, and drying at 100 ℃ overnight to obtain polyimide;
s3, adding 1g of silica microspheres with surface hydroxylation modification into 60mL of anhydrous N, N-dimethylacetamide (DMAc) for uniform ultrasonic dispersion, adding 10g of the polyimide, stirring and mixing for 2h to obtain a mixture solution, performing vacuum defoaming treatment on the mixture solution, coating the mixture solution on a glass plate, treating the mixture solution at 60 ℃ for 30min, drying the mixture solution at 150 ℃ for 60min, peeling the mixture from the glass plate, fixing the mixture solution on a metal frame, placing the metal frame in a vacuum drying oven, treating the mixture solution at 280 ℃ for 60min, and cooling to obtain the polyimide film, wherein the thickness of the polyimide film is controlled to be 50 microns.
Comparative example 1
A high-modulus high-hardness polyimide film is prepared by the following steps:
s1, adding 2.0mL of ammonia water (25%) into 30mL of ethanol water solution with the volume ratio of 4:1, uniformly stirring, adding 30mL of anhydrous ethanol in which 1.1mL of tetraethoxysilane is dissolved, stirring for reacting for 5 hours to obtain silicon dioxide microsphere sol, washing, filtering, and drying at 60 ℃ for 12 hours to obtain silicon dioxide microspheres;
s2, under nitrogen atmosphere, adding 12.6g (100mmol) of 2, 5-diaminopyrimidin-4 (3H) -ketone into 200mL of anhydrous N, N-dimethylacetamide (DMAc) and uniformly stirring, then adding 44.4g (100mol) of 4, 4' - (hexafluoroisopropylene) diphthalic anhydride and stirring for reaction for 3 hours at room temperature to obtain a polyamic acid solution; continuously stirring the polyamic acid solution for 6 hours, adding 6.5mL of pyridine serving as an imidizing agent, adding 19.5mL of acetic anhydride serving as a dehydrating agent after complete dispersion, stirring for reaction for 3 hours, adding the obtained reaction solution into ethanol for precipitation, filtering, and drying at 100 ℃ overnight to obtain polyimide;
s3, adding 1g of silica microspheres into 60mL of anhydrous N, N-dimethylacetamide (DMAc), performing ultrasonic dispersion uniformly, adding 10g of the polyimide, stirring and mixing for 2h to obtain a mixture solution, performing vacuum defoaming treatment on the mixture solution, coating the mixture solution on a glass plate, treating at 60 ℃ for 30min, drying at 150 ℃ for 60min, peeling off the glass plate, fixing the glass plate on a metal frame, treating at 280 ℃ for 60min, and cooling to obtain the polyimide film, wherein the thickness of the polyimide film is controlled to be 50 microns.
Comparative example 2
A high-modulus high-hardness polyimide film is prepared by the following steps:
s1, adding 2.0mL of ammonia water (25%) into 30mL of ethanol water solution with the volume ratio of 4:1, uniformly stirring, adding 30mL of anhydrous ethanol in which 1.1mL of tetraethoxysilane is dissolved, stirring for reacting for 5 hours to obtain silicon dioxide microsphere sol, washing, filtering, and drying at 60 ℃ for 12 hours to obtain silicon dioxide microspheres;
adding 1g of silicon dioxide microspheres into 10mL of sodium hydroxide aqueous solution (10 wt%), stirring in a water bath at 80 ℃ for reaction for 2h, cooling to room temperature after the reaction is finished, filtering, washing with water, and drying at 60 ℃ for 12h to obtain surface-hydroxylated modified silicon dioxide microspheres;
s2, under the nitrogen atmosphere, adding 20.0g (100mmol) of 4, 4 '-diaminodiphenyl ether into 200mL of anhydrous N, N-dimethylacetamide (DMAc) and uniformly stirring, then adding 44.4g (100mol) of 4, 4' - (hexafluoroisopropylene) diphthalic anhydride and stirring for reaction for 3 hours at room temperature to obtain a polyamic acid solution; continuously stirring the polyamic acid solution for 6 hours, adding 6.5mL of pyridine serving as an imidizing agent, adding 19.5mL of acetic anhydride serving as a dehydrating agent after complete dispersion, stirring for reaction for 3 hours, adding the obtained reaction solution into ethanol for precipitation, filtering, and drying at 100 ℃ overnight to obtain polyimide;
s3, adding 1g of silica microspheres with surface hydroxylation modification into 60mL of anhydrous N, N-dimethylacetamide (DMAc) for uniform ultrasonic dispersion, adding 10g of the polyimide, stirring and mixing for 2h to obtain a mixture solution, performing vacuum defoaming treatment on the mixture solution, coating the mixture solution on a glass plate, treating the mixture solution at 60 ℃ for 30min, drying the mixture solution at 150 ℃ for 60min, peeling the mixture from the glass plate, fixing the mixture solution on a metal frame, placing the metal frame in a vacuum drying oven, treating the mixture solution at 280 ℃ for 60min, and cooling to obtain the polyimide film, wherein the thickness of the polyimide film is controlled to be 50 microns.
The polyimide films obtained in examples and comparative examples were subjected to performance tests shown in the following methods, and the results are shown in table 1.
Testing the thermal linear expansion coefficient by using a thermal mechanical analyzer under the conditions of a nitrogen atmosphere, a temperature range of 50-300 ℃ and a heating rate of 10 ℃/min;
surface hardness, measured using a pencil hardness tester according to ASTM D3363 film hardness test (pencil method);
the heat shrinkage was measured using a heat shrinkage tester (200 ℃ C.) according to GB/T13542.2-2009, part 2 of film for electrical insulation;
the modulus of elasticity is measured at room temperature at 25 ℃ in accordance with standard ASTM D882 using a film tensile tester.
TABLE 1 test results of polyimide films obtained in examples 1 to 5 and comparative examples 1 to 2
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. The high-modulus high-hardness polyimide film is characterized by comprising a polyimide matrix and silica microspheres dispersed in the polyimide matrix;
the polyimide is obtained by performing polycondensation reaction on a diamine monomer containing pyrimidone diamine and tetracarboxylic dianhydride, and the silica microspheres are silica microspheres with surface hydroxylation modification;
the pyrimidone diamine is 2, 5-diaminopyrimidin-4 (3H) -one;
the diamine monomer also comprises aromatic diamine, and the molar ratio of the pyrimidone diamine to the aromatic diamine is 1: 0.5-4.
2. The high modulus, high stiffness polyimide film as claimed in claim 1, wherein the silica microspheres are 1-28 wt% of the polyimide weight.
3. The high modulus, high stiffness polyimide film according to claim 1 or 2, wherein the aromatic diamine is at least one of 4, 4' -diaminodiphenyl ether, 1, 3-bis (4' -aminophenoxy) benzene, 4' -diaminodiphenyl sulfide, 4' -diaminodiphenylmethane, 3' -diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfone, or 4, 4' -diaminobenzophenone.
4. The high modulus, high hardness polyimide film according to claim 1 or 2, wherein said tetracarboxylic dianhydride is at least one of 4, 4'- (hexafluoroisopropylidene) diphthalic anhydride, 3, 3', 4, 4 '-biphenyltetracarboxylic dianhydride, 4, 4' -oxydiphthalic dianhydride, 2', 3, 3' -benzophenonetetracarboxylic dianhydride, 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride or 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride.
5. The high modulus, high hardness polyimide film according to claim 3, wherein said tetracarboxylic dianhydride is at least one of 4, 4'- (hexafluoroisopropylene) diphthalic anhydride, 3, 3', 4, 4 '-biphenyltetracarboxylic dianhydride, 4, 4' -oxydiphthalic dianhydride, 2', 3, 3' -benzophenonetetracarboxylic dianhydride, 1, 2, 3, 4-cyclobutanetetracarboxylic dianhydride, or 1, 2, 4, 5-cyclohexanetetracarboxylic dianhydride.
6. The high modulus high hardness polyimide film according to claim 1 or 2, wherein the surface-hydroxylated-modified silica microspheres are obtained by reacting silica microspheres with a base compound.
7. The high modulus, high stiffness polyimide film as claimed in claim 6, wherein the base compound is sodium hydroxide or potassium hydroxide.
8. The high modulus, high stiffness polyimide film according to claim 1 or 2, which is prepared by the following method: performing polycondensation reaction on a diamine monomer containing pyrimidone diamine and tetracarboxylic dianhydride to obtain polyimide, fully mixing the polyimide and the silica microspheres with surface hydroxylation modification, and forming a film to obtain the polyimide film.
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| CN111808306A (en) * | 2020-06-16 | 2020-10-23 | 浙江中科玖源新材料有限公司 | Polyimide film with low thermal expansion coefficient and preparation method thereof |
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| RU2335335C2 (en) * | 2006-09-19 | 2008-10-10 | Государственный научно-исследовательский институт особо чистых биопрепаратов | Ultra-filtrating heat and chemical resistant polyimide membrane and method of its |
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| US5006636A (en) * | 1988-01-28 | 1991-04-09 | Bayer Aktiengesellschaft | Process for the production of SiO2 containing polybenzamides |
| JP2000063515A (en) * | 1998-08-21 | 2000-02-29 | Jsr Corp | Polyamic acid, polyimide and liquid crystal aligning agent |
| CN111808423A (en) * | 2020-06-16 | 2020-10-23 | 浙江中科玖源新材料有限公司 | Polyimide film with high heat resistance and low thermal expansion coefficient and preparation method thereof |
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Denomination of invention: A high modulus and high hardness polyimide film Effective date of registration: 20231114 Granted publication date: 20220520 Pledgee: China Merchants Bank Co.,Ltd. Jinhua Branch Pledgor: Zhejiang Zhongke Jiuyuan New Material Co.,Ltd. Registration number: Y2023980065179 |